CN116217334A - Lycopene crystal and preparation method and application thereof - Google Patents
Lycopene crystal and preparation method and application thereof Download PDFInfo
- Publication number
- CN116217334A CN116217334A CN202211734267.4A CN202211734267A CN116217334A CN 116217334 A CN116217334 A CN 116217334A CN 202211734267 A CN202211734267 A CN 202211734267A CN 116217334 A CN116217334 A CN 116217334A
- Authority
- CN
- China
- Prior art keywords
- lycopene
- crystal
- solvent
- color parameter
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 241
- OAIJSZIZWZSQBC-GYZMGTAESA-N lycopene Chemical compound CC(C)=CCC\C(C)=C\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C=C(/C)CCC=C(C)C OAIJSZIZWZSQBC-GYZMGTAESA-N 0.000 title claims abstract description 179
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 title claims abstract description 161
- JEVVKJMRZMXFBT-XWDZUXABSA-N Lycophyll Natural products OC/C(=C/CC/C(=C\C=C\C(=C/C=C/C(=C\C=C\C=C(/C=C/C=C(\C=C\C=C(/CC/C=C(/CO)\C)\C)/C)\C)/C)\C)/C)/C JEVVKJMRZMXFBT-XWDZUXABSA-N 0.000 title claims abstract description 161
- 235000012661 lycopene Nutrition 0.000 title claims abstract description 161
- 229960004999 lycopene Drugs 0.000 title claims abstract description 161
- 239000001751 lycopene Substances 0.000 title claims abstract description 161
- ZCIHMQAPACOQHT-ZGMPDRQDSA-N trans-isorenieratene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/c1c(C)ccc(C)c1C)C=CC=C(/C)C=Cc2c(C)ccc(C)c2C ZCIHMQAPACOQHT-ZGMPDRQDSA-N 0.000 title claims abstract description 161
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 235000013305 food Nutrition 0.000 claims abstract description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 55
- 239000002904 solvent Substances 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 29
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- OAIJSZIZWZSQBC-OUUYXACASA-N cis-lycopene Natural products CC(=CCCC(=CC=CC(=C/C=C/C(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C=C(C)/CCC=C(C)C)/C)C)C)C OAIJSZIZWZSQBC-OUUYXACASA-N 0.000 claims description 15
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 150000002576 ketones Chemical class 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical group CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 235000015067 sauces Nutrition 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229940017144 n-butyl lactate Drugs 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 241000227653 Lycopersicon Species 0.000 claims 5
- 235000013361 beverage Nutrition 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000047 product Substances 0.000 description 14
- 239000012053 oil suspension Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 240000003768 Solanum lycopersicum Species 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 235000020238 sunflower seed Nutrition 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000012738 dissolution medium Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 208000002249 Diabetes Complications Diseases 0.000 description 1
- 206010012655 Diabetic complications Diseases 0.000 description 1
- 238000010268 HPLC based assay Methods 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 229940096898 glyceryl palmitate Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/21—Alkatrienes; Alkatetraenes; Other alkapolyenes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Preparation or treatment thereof
- A23L2/52—Adding ingredients
- A23L2/58—Colouring agents
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/105—Plant extracts, their artificial duplicates or their derivatives
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/40—Colouring or decolouring of foods
- A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
- A23L5/43—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
- A23L5/44—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives using carotenoids or xanthophylls
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Botany (AREA)
- Mycology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of crystal preparation, and particularly discloses a lycopene crystal, and a preparation method and application thereof. The lycopene crystal of the present invention has 5 diffraction peaks with an area intensity of > 20% at the following diffraction angles 2θ:5.20 + -0.20 deg., 16.24 + -0.20 deg., 20.84 + -0.20 deg., 22.27 + -0.20 deg., 24.55 + -0.20 deg.. The crystal has the advantages of remarkably improved product quality and utilization rate, high purity, strong stability and bright color, and is suitable for being applied to foods and beverages.
Description
Technical Field
The invention relates to the technical field of crystal preparation, in particular to a lycopene crystal, and a preparation method and application thereof.
Background
Lycopene is one of carotenoid, contains many double bonds in the molecule, has strong antioxidant activity, and can prevent prostate cancer and breast cancer, enhance organism immunity, protect liver and relieve diabetic complications. It has been identified as a type A nutrient and can be used as a food additive with dual functions of nutrition and coloring. Lycopene in food raw materials mainly exists in a total reflection configuration, wherein the lycopene with a cis structure has higher bioactivity and bioavailability and is easier to be absorbed and utilized by human bodies.
Different polymorphs of the same compound have different lattice structures and energies and exhibit different chemical and physical properties. In food production, the purity, nature, crystallinity and morphology of crystals all affect their bioavailability, stability and coloration properties as food processing materials and during formulation processing.
At present, lycopene is mainly added into food or beverage in the form of lycopene oil and lycopene water-soluble preparation, and lycopene crystals prepared industrially have low purity, large particle size difference, low crystallinity, and problems of crystal coalescence, solvent encapsulation and the like, and meanwhile, the crystals are black red and low in color saturation, which seriously affects the use of lycopene in the production of lycopene preparation.
Therefore, there is a need to develop a process for preparing lycopene crystal raw materials with better long-term stability and colorant properties.
Disclosure of Invention
The invention provides the lycopene crystal which has high purity, high crystallinity and complete crystal form, and has high stability, high solubility and bright color after forming oil-soluble and water-soluble preparations.
In order to achieve the object, the technical scheme of the invention is as follows:
a lycopene crystal having 5 diffraction peaks with an area intensity of > 20% of the diffraction peaks, said diffraction peaks being located at the following diffraction angles 2θ:5.20 + -0.20 deg., 16.24 + -0.20 deg., 20.84 + -0.20 deg., 22.27 + -0.20 deg., 24.55 + -0.20 deg..
The diffraction peak area intensity refers to the percentage ratio of the diffraction peak area to the maximum diffraction peak area.
The lycopene crystal of the present invention has diffraction peaks in an X-ray powder diffraction pattern at least at the following diffraction angles 2 theta: 5.20.+ -. 0.20 °, 6.87.+ -. 0.20 °, 12.17.+ -. 0.20 °, 15.10.+ -. 0.20 °, 15.65.+ -. 0.20 °, 16.24.+ -. 0.20 °, 17.40.+ -. 0.20 °, 18.34.+ -. 0.20 °, 18.85.+ -. 0.20 °, 19.33.+ -. 0.20 °, 20.84.+ -. 0.20 °, 21.51.+ -. 0.20 °, 22.27.+ -. 0.20 °, 22.74.+ -. 0.20 °, 24.55.+ -. 0.20 °, 26.24.+ -. 0.20 °, 27.56.+ -. 0.20 °, 28.74.+ -. 0.20 °, 29.52.+ -. 0.20 °.
The particle size D10 of the lycopene crystal is 0.2-1.0 mu m, the D50 is 0.8-4.0 mu m, and the D90 is 1.2-10.0 mu m.
The color parameter L of the lycopene crystal is 39-44, the color parameter a is 16-24, the color parameter b is 6-9, the color parameter c is 20-25, and the color parameter h is 15-20.
The lycopene content in the lycopene crystal is above 97%, the cis-lycopene accounts for 2-10%, and the insoluble content of dichloromethane accounts for less than or equal to 0.15%.
In the invention, key color parameters of lycopene crystal are measured by a reflected light mode of a spectrocolorimeter, wherein L is a measurement of sample brightness, 0 is black, 100 is white, and gray is between 0 and 100; a represents red-green, positive values are red (the greater the positive value, the higher the red saturation) and negative values are green; b represents yellow blue, positive values are yellow, negative values are blue. The c value reflects the color saturation or purity, the greater the chromaticity, the more vivid the color. The h parameter (hue angle) is calculated from the a and b values. The larger the a value is, the smaller the b value is, the lower the h value is, and the crystal color is bright red.
Through repeated researches, the lycopene crystal is obtained, has characteristics on an X-ray diffraction pattern, crystal particle size and color of the crystal, has obvious improvement on product quality and utilization rate, has high purity and high stability, has bright color, and is suitable for being applied to foods and beverages.
The lycopene crystals of the present invention have an X-ray powder diffraction pattern substantially as shown in fig. 1, or an X-ray powder diffraction pattern substantially the same as the X-ray powder diffraction pattern shown in fig. 1.
Preferably, the particle size D10 of the lycopene crystal is 0.3-0.95 mu m, D50 is 1-4.0 mu m, and D90 is 1.8-9.0 mu m;
the color parameter L is 39-44, the color parameter a is 18-22, the color parameter b is 6-8, the color parameter c is 20-23, and the color parameter h is 16-20;
the lycopene content in the lycopene crystal is 97-99%, the cis-lycopene accounts for 4-8.5%, and the methylene dichloride insoluble substance accounts for 0.05-0.15%;
and/or, the X-ray powder diffraction pattern of the lycopene crystal is shown in figure 1.
Preferably, in the X-ray powder diffraction pattern, the diffraction angle 2 theta is 24.55+/-0.20 DEG, the diffraction peak intensity is maximum, the d value is 3.62+/-0.06A, and the peak shape is sharp and clear.
The invention also provides a method for preparing the lycopene crystal, which comprises the following steps:
(1) Dissolving lycopene crystal raw material in crystallization solvent; the crystallization solvent is an ester solvent, a ketone solvent or a mixed solvent of the ester solvent and the ketone solvent; the ester solvent is one or more of ethyl acetate, butyl acetate, n-butyl lactate and methyl acetate, and the ketone solvent is one or more of acetone, methyl ethyl ketone and cyclohexanone; the volume ratio of the ester solvent to the ketone solvent in the mixed solvent is (1-3) 1;
(2) Cooling to 40-45deg.C at 25-30deg.C/h, preferably 38-42deg.C, standing, maintaining the temperature for 1-2 hr, preferably 0.8-1.2 hr (until a large amount of needle-like crystals appear);
(3) Cooling to 25-30deg.C at 3-5deg.C/h, stirring, maintaining the temperature for 4-5 hr, preferably 3.5-4.5 hr, and stirring at 250-300rpm.
Preferably, the crystallization solvent is ethyl acetate, methyl acetate or a mixed solvent of acetone and ethyl acetate in a volume ratio of 1:1;
and/or the mass-to-volume ratio of the lycopene crystal raw material to the crystallization solvent is 1: (25-30) g/mL;
and/or the lycopene crystal raw material is lycopene crystal prepared by taking tomatoes or processed products thereof as raw materials, extracting with an organic solvent, concentrating and crystallizing, wherein the processed products comprise tomato homogenate, tomato sauce, tomato peel or peel slag generated in the processing process of the tomato sauce; the organic solvent is a mixed solvent of an alkane solvent and a low-molecular ketone solvent, the alkane solvent is n-hexane, the low-molecular ketone solvent is butanone or acetone, and the volume ratio of the alkane solvent to the low-molecular ketone solvent is 1: (3-6); preferably, the particle size requirements of the lycopene crystal raw material are as follows: d10 < 10 μm, D50 < 20 μm, D90 < 50 μm;
and/or the temperature of dissolution in the step (1) is 60-65 ℃, the dissolution is carried out for 1-2 hours under stirring, and the stirring rotating speed is 250-300rpm;
and/or, after the step (3), further comprising the steps of filtering, washing and vacuum drying at 60-70 ℃.
The method of the invention is simple in realization, high in efficiency and high in yield, and is suitable for mass industrialized production of the lycopene crystal.
According to the research of the invention, when the lycopene crystal prepared by the method is applied to lycopene oil, the lycopene crystal has good solubility, high viscosity, enhanced stability and bright color; when the lycopene water-soluble preparation is applied to lycopene water-soluble preparations, the particle size of the product is small, the stability is enhanced, the color tone is stable, and the lycopene water-soluble preparation is more suitable for being applied to foods and beverages.
Furthermore, the invention also provides the lycopene crystal, or the application of the lycopene crystal prepared by the method in the preparation of lycopene-containing products.
And a product comprising the lycopene crystals described above, or lycopene crystals prepared by the above method; preferably, the product is a food product, more preferably a beverage.
The invention has the advantages that:
(1) The lycopene provided by the invention has the crystal content of more than 97%, the insoluble content of dichloromethane is less than or equal to 0.15%, the crystal purity is high, the impurity content is less, and the cis-lycopene content is 2-10%.
(2) The lycopene crystal provided by the invention has the average particle size of 0.7-4.0 mu m, high crystallinity, complete crystal form and few diffraction peaks, is used for lycopene preparation application, improves product stability, increases solubility, has bright color, and is more suitable for application in foods and beverages.
(3) The preparation method has the advantages of mild condition, greatly reduced solvent consumption, high crystal yield, low production cost and wider application range, and is more suitable for large-scale production.
Drawings
FIG. 1 is an X-ray powder diffraction pattern (XRD) of lycopene crystals prepared in example 1 of the present invention.
Figure 2 is an X-ray powder diffraction pattern (XRD) of a lycopene crystal raw material for producing lycopene crystals of the present invention prepared in example 1 of the present invention.
FIG. 3 is a photograph of an oil suspension of example 1 in experimental example of the present invention.
FIG. 4 is a photograph showing the color of the oil suspension of comparative example 1 in the experimental example of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents and the like used in the examples below, unless otherwise indicated, are all those available commercially or may be prepared by methods conventional in the art.
The method for detecting the content of lycopene crystals is disclosed in the invention, namely, lycopene which is a plant extract of T/CCCMHPIE 1.28-2018.
The cis-lycopene content detection method comprises the following steps: HPLC assay, chromatographic column: ultimateXB-C30 column (250 m. Times.4.6 mm,5 μm); gradient conditions: 0-20 min, wherein the A phase is reduced from 100% to 50%, 20-40 min, and the A phase is kept at 50%; the flow rate is 1mL/min; the sample injection amount is 10 mu L; mobile phase: a (methanol: acetonitrile=25:75, v: v), mobile phase B (methyl tert-butyl ether: 100%), column temperature 25 ℃, detection wavelength 472nm.
The method for detecting the content of the insoluble matters in the dichloromethane comprises the following steps: weighing lycopene crystal about 5.0000g, and weighing m 1 Adding dichloromethane 500mL, ultrasonic treating at 100HZ frequency for 10min to obtain solution, and drying 0.22 μm microporous filter membrane at 60deg.C to constant weight m ,2 (accurate to 0.0000 g), filtering the solution with filter membrane under negative pressure, and drying the filter membrane at 60deg.C to constant weight m 3 (accurate to 0.0000 g) and calculated to give crystalline dichloromethane insoluble content: (m) 3 -m 2 )/m 1 *100％。
XRD detection device: the D8ADVANCEX ray line shooter has the following detection conditions: the X-ray source is a CuKa line, the voltage is 40kV, the current is 30.0mA, the scanning angle (2 theta) is 5-90 degrees, and the scanning speed is 4/min.
Method for detecting crystal grain size in examples and comparative examples of the present invention: weighing 0.2g to 50g of crystal in sunflower seed oil, and carrying out ultrasonic treatment at 100HZ for 10min to uniformly disperse the crystal in the sunflower seed oil. Particle size detection was performed using an LS900 laser particle size analyzer.
Example 1
The embodiment provides a preparation method of lycopene crystal, which comprises the following steps:
taking 5kg of tomato peel residues, respectively adding 5L of normal hexane and 20L of acetone, stirring and extracting for 4 times at 45 ℃, merging the extracting solutions, concentrating under reduced pressure until crystals are separated out, filtering the concentrated solution, and drying in vacuum to obtain lycopene crystals which are used as raw materials for subsequent production of lycopene crystals. The content of the crystal lycopene is 95.2%, the granularity D10 is 2.34 mu m, the granularity D50 is 5.49 mu m, the granularity D90 is 9.49 mu m, the crystal tone value L is 41.19, the crystal tone value a is 12.95, the crystal tone value b is 5.38, the crystal tone value c is 14.02, and the crystal tone value h is 22.56. In the X-ray powder diffraction pattern, there are a plurality of diffraction peaks with an area intensity of > 20% which are located in particular at the following diffraction angles 2θ:5.31 °, 14.98 °, 15.63 °, 16.16 °, 17.34 °, 21.55 °, 22.00 °, 24.36 °, 25.95 °. The X-ray powder diffraction pattern of the specific raw materials is shown in figure 2, and the main information is shown in table 1.
TABLE 1
Taking 100g of the lycopene crystal raw material, adding 27 times of ethyl acetate (namely, adding 27mL of ethyl acetate per gram of lycopene crystal) into the lycopene crystal raw material, dissolving the lycopene crystal raw material at 63 ℃ for 2 hours, stirring the lycopene crystal raw material at 300rpm, reducing the temperature to 40 ℃ at a speed of 25 ℃/h, standing, preserving heat and growing the crystal for 1 hour until a large number of needle-shaped crystals appear. Then cooling to 30 ℃ according to the cooling rate of 3 ℃/h, stirring, preserving heat and growing crystals for 4 hours, wherein the stirring rotating speed is 300rpm. After the crystallization liquid is filtered by suction, 100mL ethyl acetate is used for washing for 2 times, and wet crystals are dried in vacuum at 60 ℃ for 12 hours to obtain lycopene crystals. The X-ray powder diffraction pattern of the crystal is shown in figure 1, in the X-ray powder diffraction pattern, there are 5 diffraction peaks with the area intensity of more than 20%, and the diffraction peaks are specifically positioned at the following diffraction angles 2 theta: the diffraction peak intensity at the diffraction angle 2 theta of 24.55 degrees is maximum, the d value is 3.62A, and the peak shape is sharp and clear, wherein the diffraction angle is 5.20 degrees, 16.24 degrees, 20.84 degrees, 22.27 degrees and 24.55 degrees. The main information in the diffraction pattern of fig. 1 is shown in table 2.
TABLE 2
The content of lycopene in the crystal is 98.7%, the cis-lycopene content is 8.4%, the content of dichloromethane insoluble matter is 0.05%, the crystal granularity D10 is 0.71 μm, the D50 is 1.07 μm, and the D90 is 1.80 μm. The key color parameters of the prepared crystal are measured by a spectrocolorimeter reflection light mode, and the color tone value L of the crystal is 39.15, a is 20.15, b is 6.14, c is 20.97 and h is 16.95. The content yield of the crystal lycopene is 98.76%.
Example 2
The embodiment provides a preparation method of lycopene crystal, which comprises the following steps:
taking 5kg of tomato peel residues, respectively adding 5L of normal hexane and 25L of acetone, stirring and extracting for 4 times at 45 ℃, merging the extracting solutions, concentrating under reduced pressure until crystals are separated out, filtering the concentrated solution, and drying in vacuum to obtain lycopene crystals which are used as raw materials for subsequent production of lycopene crystals. The content of the crystal lycopene is 94.2%, the granularity D10 is 5.42 mu m, the granularity D50 is 11.68 mu m, the granularity D90 is 22.49 mu m, the crystal tone value L is 39.81, a is 13.42, b is 5.86, c is 14.64, and h is 23.64. In the X-ray powder diffraction pattern, there are a plurality of diffraction peaks with an area intensity of > 20% which are located in particular at the following diffraction angles 2θ:5.28 °, 14.93 °, 16.04 °, 17.12 °, 18.75 °, 21.98 °, 23.87 °, 24.34 °, 25.91 °.
Taking 100g of the lycopene crystal raw material, adding 30 times of methyl acetate (namely, 30mL of methyl acetate is added per gram of the lycopene crystal raw material), dissolving at 63 ℃ for 2 hours, stirring at 300rpm, reducing the temperature to 40 ℃ at the speed of 25 ℃/h, standing, preserving heat and growing the crystal for 1 hour until a large number of needle-shaped crystals appear. Then cooling to 30 ℃ according to the cooling rate of 5 ℃/h, stirring, preserving heat and growing crystals for 4 hours, wherein the stirring rotating speed is 280rpm. After the crystallization liquid is filtered by suction, 100mL of methyl acetate is used for washing for 2 times, and wet crystals are dried in vacuum for 12 hours at 65 ℃ to obtain lycopene crystals. The XRD patterns are compared by research, the diffraction angle 2 theta of each diffraction peak is within +/-0.20 degrees of the crystal form of the example 1, the area intensity of each diffraction peak is equivalent to that of the crystal form of the example 1, and the product is determined to be the crystal form of the example 1. In the X-ray powder diffraction pattern, the crystal has 5 diffraction peaks with the area intensity of more than 20 percent, and the diffraction peaks are specifically positioned at the following diffraction angles 2 theta: the diffraction peak intensity at the diffraction angle 2 theta of 24.48 degrees is maximum, the d value is 3.64A, and the peak shape is sharp and clear. Lycopene content of 98.4%, cis-lycopene content of 5.1%, and diThe ratio of chloromethane insoluble matters is 0.15%, the crystal granularity D10 is 0.84m, the D50 is 2.50 mu m, and the D90 is 5.01 mu m; key color parameters of the prepared crystal are measured by a spectrocolorimeter in a reflected light mode, and the color tone value of the crystal is L * 43.79，a * 18.67，b * 6.68，c * 21.69，h * 18.69. The content yield of the crystal lycopene is 98.57%.
Example 3
The embodiment provides a preparation method of lycopene crystal, which comprises the following steps:
taking 5kg of tomato peel residues, respectively adding 5L of normal hexane and 30L of acetone, stirring and extracting for 4 times at 45 ℃, merging the extracting solutions, concentrating under reduced pressure until crystals are separated out, filtering the concentrated solution, and drying in vacuum to obtain lycopene crystals which are used as raw materials for subsequent production of lycopene crystals. Crystalline lycopene content 93.2%, particle size D10 8.13 μm, D50 18.49 μm, D90 42.18 μm. Crystal tone values l.39.54, a.13.51, b.5.25, c.14.49, h.21.23. In the X-ray powder diffraction pattern, there are a plurality of diffraction peaks with an area intensity of > 20% which are located in particular at the following diffraction angles 2θ:5.34 °, 15.05 °, 16.13 °, 17.25 °, 18.78 °, 22.04 °, 23.85 °, 24.31 °, 26.01 °.
Taking 100g of the lycopene crystal raw material, adding a mixed solvent with the volume ratio of 25 times of acetone to ethyl acetate being 1:1 (namely, adding 25mL of the mixed solvent into each gram of lycopene crystal raw material), dissolving at 60 ℃ for 2 hours, stirring at the speed of 250rpm, reducing the temperature to 40 ℃ according to the speed of 30 ℃/h, standing, preserving the temperature, and growing the crystal for 1 hour until a large number of needle-shaped crystals appear. Then cooling to 28 ℃ according to the cooling rate of 5 ℃/h, stirring, preserving heat and growing crystals for 4 hours, wherein the stirring rotating speed is 250rpm. After the crystallization liquid is filtered, the mixed solvent of 100mL of acetone and ethyl acetate with the volume ratio of 1:1 is used for washing for 2 times, and wet crystals are dried in vacuum for 12 hours at 65 ℃ to obtain lycopene crystals. The XRD patterns are compared by research, the diffraction angle 2 theta of each diffraction peak is within +/-0.20 degrees of the crystal form of the example 1, the area intensity of each diffraction peak is equivalent to that of the crystal form of the example 1, and the product is determined to be the crystal form of the example 1. The crystal has 5 diffraction peak area intensities in an X-ray powder diffraction pattern20% of the diffraction peaks, which are located in particular at the following diffraction angles 2θ: the diffraction peak intensity at the diffraction angle 2 theta of 24.67 degrees is maximum, the d value is 3.58A, and the peak shape is sharp and clear, wherein the diffraction angle is 5.40 degrees, 16.38 degrees, 21.03 degrees, 22.45 degrees and 24.67 degrees. The content of crystal lycopene is 97.6%, the cis-lycopene accounts for 4.2%, the content of dichloromethane insoluble substances accounts for 0.11%, the crystal granularity D10 is 0.91 μm, the D50 is 3.77 μm, and the D90 is 8.80 μm; key color parameters of the prepared crystal are measured by a spectrocolorimeter in a reflected light mode, and the color tone value of the crystal is L * 42.78, a.21.63, b.7.63, c.22.94, h.19.43. The content yield of the crystal lycopene is 98.85%.
Comparative example 1
This comparative example provides a process for the preparation of lycopene crystals, which is identical to example 1, with the only difference that: the recrystallization solvent replaced ethyl acetate with 90% ethanol. The crystals finally obtained have, in an X-ray powder diffraction pattern, a plurality of diffraction peaks with an area intensity of > 20% of the diffraction peaks, which are located in particular at the following diffraction angles 2 theta: 6.91 °, 10.54 °, 15.15 °, 16.98 °, 18.11 °,20.45 °, 22.43 °, 23.81 °, 24.47 °, 27.84 °. The content of crystal lycopene is 95.3%, the cis-lycopene accounts for 1.78%, the content of dichloromethane insoluble substances accounts for 0.35%, the crystal granularity D10 is 1.98 μm, the D50 is 4.97 μm, and the D90 is 10.47 μm; the key color parameters of the prepared crystals are measured by a spectrocolorimeter reflection light mode, and the color tone values of the crystals are L.42.76, a.14.54, b.5.63, c.16.57 and h.21.17. The content yield of the crystal lycopene is 96.80%.
After the crystallization solvent is changed into ethanol, the crystal form of the crystal is changed, the crystal content and cis proportion are not obviously improved, and the indexes of the crystal color and granularity are not ideal.
Comparative example 2
This comparative example provides a process for the preparation of lycopene crystals, which is identical to example 3, with the only difference that: the recrystallization solvent is changed into ethyl acetate with the volume ratio of 1:2: the mixed solvent of acetone replaces the mixed solvent of acetone and ethyl acetate with the volume ratio of 1:1. The crystals finally obtained have, in an X-ray powder diffraction pattern, a plurality of diffraction peaks with an area intensity of > 20% of the diffraction peaks, which are located in particular at the following diffraction angles 2 theta: 5.41 °, 14.14 °, 15.03 °, 16.18 °, 18.50 °, 21.51 °, 22.74 °. The content of crystal lycopene is 95.41%, the cis-lycopene accounts for 2.15%, the content of dichloromethane insoluble substances accounts for 0.21%, the crystal granularity D10 is 3.28 μm, the D50 is 8.42 μm, and the D90 is 15.34 μm; the key color parameters of the prepared crystal are measured by a spectrocolorimeter reflection light mode, and the color tone value L of the crystal is 39.88, a is 14.12, b is 5.85, c is 15.66 and h is 22.5. The content yield of the crystal lycopene is 97.56%.
Changing the crystallization solvent to ethyl acetate with the volume ratio of 1:2: the mixed solvent of acetone has the advantages that the crystal form is changed, the crystal content and cis-form ratio are not obviously improved, and the crystal color and granularity indexes are not ideal.
Comparative example 3
This comparative example provides a method for preparing lycopene crystals, wherein the raw materials of the lycopene crystals are the same as those in example 1, and the preparation method comprises the following steps: to 100g of lycopene crystal material, 27 times of ethyl acetate was added, and the mixture was dissolved at 63℃for 2 hours at a stirring speed of 300rpm, after which the temperature was lowered to 40℃at a rate of 25℃per hour, and the crystal was grown under stirring at a stirring speed of 300rpm for 1 hour, until a large amount of crystals were present. Then cooling to 30 ℃ according to the cooling rate of 3 ℃/h, stirring, preserving heat and growing crystals for 4 hours, wherein the stirring rotating speed is 300rpm. After the crystallization liquid is filtered by suction, 100mL ethyl acetate is used for washing for 2 times, and wet crystals are dried in vacuum at 60 ℃ for 12 hours to obtain lycopene crystals. The finally prepared crystal has a plurality of diffraction peaks with the area intensity of more than 20% in an X-ray powder diffraction pattern, and the diffraction peaks are specifically positioned at the following diffraction angles 2 theta: 4.93 °, 14.65 °, 15.48 °, 16.45 °, 20.41 °, 21.55 °, 22.67 °, 23.39 °, 25.41 °. Crystalline lycopene content of 97.7%, cis lycopene content of 2.12%, dichloromethane insoluble content of 0.18%, crystal size D10 of 2.18 μm, D50 of 5.17 μm, and D90 of 16.47 μm; the key color parameters of the prepared crystals are measured by a spectrocolorimeter reflection light mode, and the color tone values of the crystals are L.40.27, a.15.40, b.6.05, c.16.33 and h.21.48. The content yield of the crystal lycopene is 97.8%.
After the primary crystal growth temperature is changed, the crystal form of the crystal is changed, the cis proportion of the crystal is not obviously improved, and the grain size index is not ideal.
Comparative example 4
This comparative example provides a method for preparing lycopene crystals, wherein the raw materials of the lycopene crystals are the same as those in example 1, and the preparation method comprises the following steps: adding 27 times of ethyl acetate into 100g of lycopene crystal raw material, dissolving for 2 hours at 63 ℃, and stirring at 300rpm, then directly reducing the temperature to 25 ℃ according to the speed of 30 ℃/h, stirring, preserving heat and growing the crystal for 4 hours, wherein the stirring speed is 300rpm. After the crystallization liquid is filtered by suction, 100mL ethyl acetate is used for washing for 2 times, and wet crystals are dried in vacuum at 60 ℃ for 12 hours to obtain lycopene crystals. The finally prepared crystal has a plurality of diffraction peaks with the area intensity of more than 20% in an X-ray powder diffraction pattern, and the diffraction peaks are specifically positioned at the following diffraction angles 2 theta: 5.12 °, 14.75 °, 15.78 °, 16.85 °, 18.65 °, 20.56 °, 22.87 °, 25.14 °, 26.01 °. The content of crystal lycopene is 96.14%, the cis-lycopene accounts for 3.89%, the content of dichloromethane insoluble substances accounts for 0.41%, the crystal granularity D10 is 2.63 μm, the D50 is 7.26 μm, and the D90 is 13.88 μm; the key color parameters of the prepared crystals are measured by a spectrocolorimeter reflection light mode, and the color tone values of the crystals are L.42.36, a.16.33, b.6.25, c.16.05 and h.20.94. The content yield of the crystal lycopene is 95.14%.
After the crystal growing mode is changed, the crystal form is changed, the crystal content is not obviously improved, the content of dichloromethane insoluble substances is increased, and the yield is reduced. The crystal color and the granularity index are not ideal.
Comparative example 5
This comparative example provides a process for the preparation of lycopene crystals, which is identical to example 1, with the only difference that: after standing, preserving heat and growing crystals, cooling to 30 ℃ at a speed of 3 ℃/h, stirring, preserving heat and growing crystals for 4 hours, wherein the stirring rotating speed is 100rpm. The crystals finally obtained have, in an X-ray powder diffraction pattern, a plurality of diffraction peaks with an area intensity of > 20% of the diffraction peaks, which are located in particular at the following diffraction angles 2 theta: 5.25 °, 14.47 °, 16.91 °, 18.15 °, 20.59 °, 21.61 °, 22.65 °, 23.47 °. The content of crystal lycopene is 95.45%, the cis-lycopene accounts for 2.45%, the content of dichloromethane insoluble substances accounts for 0.31%, the crystal granularity D10 is 3.33 μm, the D50 is 8.03 μm, and the D90 is 14.10 μm; and measuring key color parameters of the prepared crystal by using a reflection light mode of a spectrocolorimeter, and measuring key color parameters of the prepared crystal by using a reflection light mode of the spectrocolorimeter, wherein the color tone values L of the crystal are 40.79, 13.70, 5.46, 13.99 and 21.73. The content yield of the crystal lycopene is 96.47%.
The secondary cooling crystallization speed is changed, the crystal form is changed, the crystal content is not obviously improved, the content of the insoluble substances of the dichloromethane is increased, and the yield is reduced. The crystal color and the granularity index are not ideal.
Example 4
This example provides a method for preparing lycopene crystals, which is identical to example 1, with the only difference that: the crystal material is lycopene crystal sold by Guangrui biological product Co., ltd, the content is 95.46%, the granularity D10 is 2.89 μm, the D50 is 5.35 μm, and the D90 is 14.19 μm. The XRD patterns of the finally prepared crystals are compared, diffraction angles 2 theta of diffraction peaks are different from the crystal form of the example 1 by +/-0.20 degrees, the area intensity of each diffraction peak is equivalent to that of the crystal form of the example 1, and the product is determined to be the crystal form of the example 1. In particular in the X-ray powder diffraction pattern, there are 5 diffraction peaks with an area intensity of > 20% of the diffraction peaks, which are located in particular at the following diffraction angles 2θ:5.36 °, 16.39 °, 20.75 °, 22.13 °, 24.60 °. The content of crystal lycopene is 98.45%, the cis-lycopene accounts for 7.89%, the content of dichloromethane insoluble substances accounts for 0.10%, the crystal granularity D10 is 0.33 μm, the D50 is 1.75 μm, and the D90 is 2.95 μm; the key color parameters of the prepared crystal are measured by a spectrocolorimeter reflection light mode, and the color tone value L of the crystal is 43.31, a is 20.95, b is 6.99, c is 22.09 and h is 18.43. The content yield of the crystal lycopene is 98.89%.
Commercial crystals are used as raw materials, the crystal forms are the same as those of the example 1, the crystal content is high, the content of dichloromethane insoluble substances is low, and the yield is high. The crystal color and granularity index are ideal.
Experimental example application evaluation detection of lycopene Crystal
The lycopene prepared in examples and comparative examples was subjected to oil preparation and water-soluble preparation application evaluation.
1. Evaluation of oil preparation
(1) Solubility evaluation
Taking about 1.0000g of lycopene crystal in a 50mL centrifuge tube, adding 50mL sunflower seed oil, ultrasonically dissolving for 30min, centrifuging for 10min at 5000rpm, taking supernatant to measure lycopene content in oil phase, and calculating solubility. The results are shown in Table 3.
Table 3 crystal solubility comparison data
(2) Stability and color contrast of oil suspension formulations
The preparation method of the lycopene oil suspension preparation comprises the following steps: mixing lycopene crystal and sunflower seed oil, and shearing with high shear emulsifying machine for 20min at 7000rpm/min to obtain lycopene oil suspension preparation with lycopene content of about 10%.
The lycopene crystals prepared in examples and comparative examples were prepared as oil suspension formulations according to the above-described methods, respectively, wherein the photographs of the color of the oil suspensions of example 1 and comparative example 1 are shown in fig. 3 and 4, respectively. The centrifugal stability and viscosity parameters were measured by sampling, and the results are shown in Table 4.
Centrifugal stability determination: 10mL of the oil suspension formulation was loaded into a 15mL centrifuge tube and centrifuged at 5000rpm for 10 minutes, and the centrifuge stability was calculated as the percentage of the volume/total volume of the formulation below centrifugation.
And (3) measuring viscosity: the lycopene oil suspension is placed in a water bath kettle at 25 ℃ for 30min, and the viscosity measurement is carried out by using an NDJ-5S digital viscometer.
Table 4 oil suspension formulation performance comparison data
| Experimental group | Centrifugal stability% | Viscosity mPa/s |
| Example 1 | 98.83 | 4888.75 |
| Example 2 | 98.01 | 4001.23 |
| Example 3 | 97.15 | 3315.87 |
| Comparative example 1 | 90.12 | 1291.74 |
| Comparative example 2 | 80.84 | 645.12 |
| Comparative example 3 | 89.56 | 1006.12 |
| Comparative example 4 | 86.41 | 891.78 |
| Comparative example 5 | 82.23 | 800.45 |
| Example 4 | 98.31 | 4678.52 |
The lycopene crystal prepared by the embodiment is applied to lycopene oil suspension preparations, and has the advantages of enhanced product stability, increased viscosity, stronger color saturation and color more similar to that of tomatoes.
2. Evaluation of Water-soluble preparation
The preparation method of the lycopene water-soluble preparation comprises the following steps:
20g of lycopene crystal, 50g of phospholipid, 50g of glyceryl palmitate, 70g of glycerol and the balance of water are mixed, heated to 75 ℃, sheared and emulsified for 15min under the condition of 8000 revolutions per minute, and then ground for 3 hours at the grinding temperature of 50 ℃ by using a nano grinder at the linear speed of 12m/s, so as to obtain the lycopene water-soluble preparation with the lycopene content of about 2%. The lycopene crystals prepared in examples and comparative examples were prepared into water-soluble preparations according to the above-mentioned methods, respectively, and the particle size, cumulative release rate, color index and stability on standing were measured by sampling. The results are shown in Table 5.
The granularity detection method comprises the following steps: the sample is weighed to be 0.5g to 50g of pure water, and is subjected to ultrasonic treatment at 100HZ for 10min, so that the crystals are uniformly dispersed in the pure water. Particle size detection was performed using an LS900 laser particle size analyzer.
The cumulative release rate detection method comprises the following steps: the dialysis bag method is adopted. 1mL of lycopene water soluble preparation is taken and put into a dialysis bag, the dialysis bag is put into a dissolution medium, and the temperature is 37 ℃ and the rotating speed is 50 r.min -1 Placing under the condition, extracting 2mL of sample solution from the dissolution cup at preset time intervals, measuring lycopene content, and supplementing corresponding bodyThe same temperature of the dissolution medium is accumulated. The dissolution medium simulates intestinal fluid (pH 6.8, PBS) and compares the effect of different dosage forms on the release rate of lycopene.
Key color parameters: weighing about 0.1g of lycopene water soluble preparation, diluting 1000 times, and measuring key color parameters of the lycopene water soluble preparation by using a reflection light mode of a spectrocolorimeter.
The method for testing the placement stability comprises the following steps: 15g of lycopene water soluble preparation is weighed into a 25mL test tube with a plug, and is subjected to light-shielding treatment by using aluminum foil paper, and after being placed in a constant temperature box at 25 ℃ for 1 month, the appearance of a sample is observed.
Table 5 comparative data on water soluble formulation properties
When the lycopene crystal prepared by the embodiment is applied to lycopene water-soluble preparations, the lycopene water-soluble preparation has small particle size, enhanced stability, good water solubility and lower h value, and the color tone is more suitable for the application of lycopene microemulsion in foods and beverages.
The results show that the lycopene crystal with the specific new crystal form prepared by the embodiment has the advantages of small granularity, high crystallinity and bright color, and can obviously improve the product performance when being applied to lycopene preparation products.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. Lycopene crystal, characterized in that in an X-ray powder diffraction pattern there are 5 diffraction peaks with an area intensity of > 20% of the diffraction peaks, said diffraction peaks being located at the following diffraction angles 2Θ:5.20 + -0.20 deg., 16.24 + -0.20 deg., 20.84 + -0.20 deg., 22.27 + -0.20 deg., 24.55 + -0.20 deg..
2. Lycopene crystal according to claim 1, characterized in that in the X-ray powder diffraction pattern there are diffraction peaks at least at the following diffraction angles 2Θ: 5.20.+ -. 0.20 °, 6.87.+ -. 0.20 °, 12.17.+ -. 0.20 ° 15.10.+ -. 0.20 °, 15.65.+ -. 0.20 °, 16.24.+ -. 0.20 °, 17.40.+ -. 0.20 °, 18.34.+ -. 0.20 °, 18.85.+ -. 0.20 °, 19.33.+ -. 0.20 °, 20.84.+ -. 0.20 °, 21.51.+ -. 0.20 °, 22.27.+ -. 0.20 °, 22.74.+ -. 0.20 °, 24.55.+ -. 0.20 °, 26.24.+ -. 0.20 °, 27.56.+ -. 0.20 °, 28.74.+ -. 0.20 °, 29.52.+ -. 0.20 °.
3. Lycopene crystal according to claim 1 or 2, characterized in that the particle size D10 of the lycopene crystal is 0.2-1.0 μm, D50 is 0.8-4.0 μm and D90 is 1.2-10.0 μm;
and/or the color parameter L of the lycopene crystal is 39-44, the color parameter a is 16-24, the color parameter b is 6-9, the color parameter c is 20-25, and the color parameter h is 15-20.
4. A lycopene crystal according to any one of claims 1-3, characterized in that the lycopene content in said lycopene crystal is above 97%, the cis-lycopene content is 2-10% and the dichloromethane insoluble content is less than or equal to 0.15%.
5. A lycopene crystal according to claim 4, characterized in that the particle size D10 of the lycopene crystal is 0.3-0.95 μm, D50 is 1-4.0 μm and D90 is 1.8-9.0 μm;
the color parameter L is 39-44, the color parameter a is 18-22, the color parameter b is 6-8, the color parameter c is 20-23, and the color parameter h is 16-20;
the lycopene content in the lycopene crystal is 97-99%, the cis-lycopene accounts for 4-8.5%, and the methylene dichloride insoluble substance accounts for 0.05-0.15%;
and/or, the X-ray powder diffraction pattern of the lycopene crystal is shown in figure 1.
6. A lycopene crystal according to claim 5, characterized in that in the X-ray powder diffraction pattern, the diffraction peak intensity at the diffraction angle 2Θ is 24.55 ± 0.20 ° is maximum, the d value is 3.62 ± 0.06A, and the peak shape is sharp and clear.
7. A method of preparing a crystal of lycopene according to any one of claims 1-6 comprising:
(1) Dissolving lycopene crystal raw material in crystallization solvent; the crystallization solvent is an ester solvent, a ketone solvent or a mixed solvent of the ester solvent and the ketone solvent; the ester solvent is one or more of ethyl acetate, butyl acetate, n-butyl lactate and methyl acetate, and the ketone solvent is one or more of acetone, methyl ethyl ketone and cyclohexanone; the volume ratio of the ester solvent to the ketone solvent in the mixed solvent is (1-3) 1;
(2) Cooling to 40-45deg.C at a rate of 25-30deg.C/h, standing, maintaining the temperature, and growing crystal for 1-2 hr;
(3) Cooling to 25-30deg.C at 3-5deg.C/h, stirring, maintaining the temperature for 4-5 hr, and stirring at 250-300rpm.
8. The method according to claim 7, wherein the crystallization solvent is ethyl acetate, methyl acetate or a mixed solvent of acetone and ethyl acetate in a volume ratio of 1:1;
and/or the mass-to-volume ratio of the lycopene crystal raw material to the crystallization solvent is 1: (25-30) g/mL;
and/or the lycopene crystal raw material is lycopene crystal prepared by taking tomatoes or processed products thereof as raw materials, extracting with an organic solvent, concentrating and crystallizing, wherein the processed products comprise tomato homogenate, tomato sauce, tomato peel or peel slag generated in the processing process of the tomato sauce; the organic solvent is a mixed solvent of an alkane solvent and a low-molecular ketone solvent, the alkane solvent is n-hexane, the low-molecular ketone solvent is butanone or acetone, and the volume ratio of the alkane solvent to the low-molecular ketone solvent is 1: (3-6); preferably, the particle size requirements of the lycopene crystal raw material are as follows: d10 < 10 μm, D50 < 20 μm, D90 < 50 μm;
and/or the temperature of dissolution in the step (1) is 60-65 ℃, the dissolution is carried out for 1-2 hours under stirring, and the stirring rotating speed is 250-300rpm;
and/or, after the step (3), further comprising the steps of filtering, washing and vacuum drying at 60-70 ℃.
9. Use of a lycopene crystal according to any one of claims 1-6, or prepared by a process according to claim 7 or 8, in the preparation of a lycopene-containing product.
10. A product comprising lycopene crystals according to any one of claims 1-6, or lycopene crystals prepared by the method of claim 7 or 8; preferably, the product is a food product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211734267.4A CN116217334A (en) | 2022-12-30 | 2022-12-30 | Lycopene crystal and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211734267.4A CN116217334A (en) | 2022-12-30 | 2022-12-30 | Lycopene crystal and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116217334A true CN116217334A (en) | 2023-06-06 |
Family
ID=86581600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211734267.4A Pending CN116217334A (en) | 2022-12-30 | 2022-12-30 | Lycopene crystal and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116217334A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176577A (en) * | 1994-10-31 | 1998-03-18 | 马克特辛姆化学工厂有限公司 | Stable lycopene concentrates and process for their preparation |
| CN1341686A (en) * | 2001-09-28 | 2002-03-27 | 新疆金企实业有限公司 | Preparation method of lycopene |
| US20150004236A1 (en) * | 2011-09-19 | 2015-01-01 | Omniactive Health Technologies Limited | Efficient process for the preparation of lycopene containing oleoresin and lycopene crystals for human consumption |
| CN110256189A (en) * | 2019-07-19 | 2019-09-20 | 长沙卫一生物科技有限公司 | The technique of lycopene is extracted from tomato peel |
| CN113200810A (en) * | 2021-04-30 | 2021-08-03 | 晨光生物科技集团股份有限公司 | Lycopene crystal and lycopene crystallization process |
-
2022
- 2022-12-30 CN CN202211734267.4A patent/CN116217334A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176577A (en) * | 1994-10-31 | 1998-03-18 | 马克特辛姆化学工厂有限公司 | Stable lycopene concentrates and process for their preparation |
| CN1341686A (en) * | 2001-09-28 | 2002-03-27 | 新疆金企实业有限公司 | Preparation method of lycopene |
| US20150004236A1 (en) * | 2011-09-19 | 2015-01-01 | Omniactive Health Technologies Limited | Efficient process for the preparation of lycopene containing oleoresin and lycopene crystals for human consumption |
| CN110256189A (en) * | 2019-07-19 | 2019-09-20 | 长沙卫一生物科技有限公司 | The technique of lycopene is extracted from tomato peel |
| CN113200810A (en) * | 2021-04-30 | 2021-08-03 | 晨光生物科技集团股份有限公司 | Lycopene crystal and lycopene crystallization process |
Non-Patent Citations (2)
| Title |
|---|
| 李芳等: "番茄红素结晶溶剂选择的初步研究", 食品工业科技, vol. 27, no. 12, 22 October 2007 (2007-10-22), pages 101 - 103 * |
| 梅晓岩等: "重结晶法提纯番茄红素的研究", 农机化研究, no. 10, 27 September 2006 (2006-09-27), pages 151 - 155 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| USRE47153E1 (en) | Genipin-rich material and its use | |
| US7582325B2 (en) | Process for the preparation of tomato extracts with high content in lycopene | |
| CN1117527C (en) | Industrial processing of tomatoes and lycopene extraction | |
| CN116217334A (en) | Lycopene crystal and preparation method and application thereof | |
| CN104136035B (en) | The method for manufacturing the extract containing zeaxanthin and/or its ester | |
| JP2019154444A (en) | Lycopene composition having improved colorant property | |
| CN111264728A (en) | White mushroom concentrated solution with high vitamin D content and preparation method thereof | |
| CN109288035A (en) | A kind of processing method of the lotus seed starch of high stability-soybean lecithin compound | |
| CN1653949A (en) | Emulsified lycopene and its preparing process | |
| CN112028767B (en) | Rosin-based antioxidant surfactant and preparation and performance thereof | |
| CN110078116A (en) | A kind of perovskite CsPbBr3Quantum dot and its preparation method and application | |
| TW201241103A (en) | Process of preparing product based on copper phthalocyanine (CuPc) particles | |
| CN114149477A (en) | Crystallization method of high-purity vitamin B12 crystal and product thereof | |
| CN107973750B (en) | Fat-soluble gardenia blue pigment and preparation method thereof | |
| CN106281321B (en) | AlP quantum dot and preparation method thereof | |
| CN114262525B (en) | Method for preparing monascus pigment nanoemulsion | |
| JP4007417B2 (en) | Novel compound, production method and use thereof | |
| CN110305495B (en) | Preparation method of oil-soluble monascus red pigment | |
| EA022851B1 (en) | Carmine food coloring composition with high stability | |
| CN107400409A (en) | It is a kind of without glimmering inner-printing ink shown and preparation method thereof | |
| CN112028733B (en) | Preparation method of high-purity lycopene | |
| CN117568020A (en) | Preparation method of bauhinia fluorescent carbon quantum dots and method for detecting quinoline yellow by using same | |
| CN105669376B (en) | Prepare crystallization processes and the application of the big inositol of high-crystallinity, partial size | |
| CN102659580B (en) | Preparation method and crystallization method of 2, 3, 5-tri-methyl hydroquinone diester new crystal | |
| CN116425896A (en) | High-yield extraction method of pinus koraiensis polysaccharide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |